Metathesis catalyst

ABSTRACT

The current invention describes new metathesis catalysts, a method for their preparation and their use in metathesis reactions.

The current invention describes new metathesis catalysts, a method for their preparation and their use.

BACKGROUND

Numerous metathesis catalysts are already known; refer to for example: Tetrahedron Lett. 1999, 40, 1091-1094, J. Am. Chem. Soc. 2000, 122, 58-71, Angew. Chem. 2003, 115, 1944-1968. It is known from these publications that substrates comprising acetal-groups considerably inhibit metathesis reactions.

DESCRIPTION

New metathesis catalysts comprising acetal-groups with the formula (I) have been found in which

-   -   Ru stands for ruthenium,     -   R1 stands for alkyl,     -   R2 stands for alkyl,     -   R3 stands for hydrogen or for an electron-withdrawing         substituent,     -   Hal stands for chlorine or bromine, independently of each other,     -   Lig stands for the ligand Lig1 or Lig2.

It was further found that the catalysts of formula (I) can be produced from compounds of formula (II)

In which R1, R2 and R3 have the above given meanings, by reaction with 2^(nd) generation Grubbs catalyst (see Aldrich Chemistry Handbook Fine Chemicals 2009-2010, page 1453) in the presence of CuCl (J. Org. Chem. 2004, 69, 6894-6896).

It was finally found out that the catalysts of formula (I) are suitable for the modification of butadiene acrylonitrile copolymers.

wherein

-   -   R4 stands for mesityl.

Especially preferred are catalysts of formula (I), in which

-   -   R1 stands for methyl or ethyl,     -   R2 stands for C6-C18 alkyl,     -   R3 stands for hydrogen or C1-C18 alkyl or stands for an         electron-withdrawing substituent from the series nitro and         SO2N(C1-C18 alkyl),     -   Hal stands for chlorine or bromine, independently of each other,     -   Lig stands for

wherein

-   -   R4 stands for mesityl.

First Exemplary Embodiment

Preparation of the catalyst of formula (I), wherein R1=Me, R2=C12H25, R3=NO2, Hal=C1, Lig=Lig1.

In a Schlenk apparatus, the 2^(nd)-generation Grubbs catalyst (0.108 g, 0.13 mmol) is mixed with a solution of compound (I-1):

(0.059 g, 0.14 mmol) in 5 ml dichloromethane and 25 mg of copper-(I)-chloride and was stirred for about 50 minutes to about 60 minutes at ambient temperature under an argon atmosphere. The solvent was then removed under vacuum and the residue was purified by column chromatography. The catalyst (I) was obtained as a green solid.

Second Exemplary Embodiment

Preparation of the catalyst of formula (I), wherein R1=Me, R2=C12H25, R3=NO2, Hal=C1, Lig=Lig1.

In a Schlenk apparatus, the 2^(nd)-generation Grubbs catalyst (0.108 g, 0.13 mmol) is mixed with a solution of compound (I-1):

(0.059 g, 0.14 mmol) in 5 ml dichloromethane and 25 mg of copper-(I)-chloride and was stirred for about 50 minutes to 60 minutes under reflux in an argon atmosphere. The solvent was then removed under vacuum and the residue stirred in ethylacetate, filtered and evaporated again. The residue was purified by column chromatography (15% ethylacetate/cyclohexane). The catalyst (I) was obtained as a green solid. 

The invention claimed is:
 1. Compounds of formula (I)

in which Ru stands for ruthenium, R1 stands for alkyl, R2 stands for alkyl, R3 stands for an electron-withdrawing substituent, Hal stands for chlorine or bromine, independently of each other, Lig stands for the ligand Lig1 or Lig2, wherein

and wherein R4 stands for mesityl.
 2. The compounds of formula (I)

wherein Ru is ruthenium, R1 is methyl or ethyl, R2 is C₆-C₁₈ alkyl, R3 is hydrogen, C₁-C₁₈ alkyl, or an electron-withdrawing substituent from the series nitro and SO₂N(C₁-C₁₈ alkyl), Hal is chlorine or bromine, independently of each other, Lig is

and wherein R4 is mesityl. 